EP0832868A2 - Method for purifying 1,1,1-tris (4-Hydroxyphenyl)-alkanes - Google Patents

Method for purifying 1,1,1-tris (4-Hydroxyphenyl)-alkanes Download PDF

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Publication number
EP0832868A2
EP0832868A2 EP97307106A EP97307106A EP0832868A2 EP 0832868 A2 EP0832868 A2 EP 0832868A2 EP 97307106 A EP97307106 A EP 97307106A EP 97307106 A EP97307106 A EP 97307106A EP 0832868 A2 EP0832868 A2 EP 0832868A2
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EP
European Patent Office
Prior art keywords
hydroxyphenyl
tris
adduct
thpe
alkane
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Granted
Application number
EP97307106A
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German (de)
French (fr)
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EP0832868A3 (en
EP0832868B1 (en
Inventor
Patrick Joseph Mccloskey
Julia Lam Lee
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SABIC Global Technologies BV
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General Electric Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification

Definitions

  • This invention relates to the purification of 1,1,1-tris(4-hydroxyphenyl)alkanes and especially 1,1,1-tris(4-hydroxyphenyl)ethane.
  • the subject compounds are useful as branching agents for polycarbonates.
  • they may be incorporated in reaction mixtures also containing dihydroxyaromatic compounds such as bisphenol A and carbonate sources such as phosgene or diphenyl carbonate.
  • the compounds are commonly prepared by the reaction of 4-hydroxyacetophenone and its homologs with phenol, said reaction being analogous to the reaction of phenol with acetone to form 2,2-bis(4-hydroxyphenyl)propane, also known as "bisphenol A”.
  • bisphenol A 2,2-bis(4-hydroxyphenyl)propane
  • THPE produced by the reaction of 4-hydroxyacetophenone with phenol can be purified by a series of washes with methanol-water variously containing at least one of THPE and sodium borohydride. In general, numerous washing steps of this type apparently need to be employed. An alternative purification method which does not require so many steps is desirable.
  • the present invention provides such an alternative purification method. It may be employed to afford a product having an APHA color number of less than 200 from a crude product containing at least about 90% THPE by weight.
  • the invention is a method for further purifying a tris(4-hydroxyphenyl)alkane of at least about 90% by weight purity which comprises:
  • the tris(4-hydroxyphenyl)alkanes which may be purified by the method of this invention include, as a genus, those compounds capable of preparation by the reaction of phenol with 4-hydroxyacetophenone and its higher homologs, such as the corresponding propiophenone and butyrophenone.
  • the preferred compound is THPE.
  • THPE having a purity of at least about 90% by weight is first obtained.
  • THPE of the required purity may be obtained by removing by-product phenol by filtration after adjusting the water content, as disclosed in the aforementioned U.S. Patent 4,992,598.
  • 2,4-pentanedione synthesis method slurrying in a chlorinated alkane such as methylene chloride followed by filtration can afford a solid product of the requisite purity.
  • the essential purification step is the formation of an adduct between THPE and a C 1-4 primary alkyl tertiary amine such as trimethylamine, triethylamine or tri-n-butylamine.
  • Triethylamine is preferred and will often be referred to hereinafter; however, it should be understood that other tertiary amines as described may be substituted therefor.
  • the adduct is formed by blending the THPE with a molar excess of the amine.
  • a typical molar ratio of amine to THPE is at least about 1.5:1, preferably at least about 2:1 and most preferably about 2.4-2.8:1.
  • the adduct thus formed comprises equimolar proportions of the amine and THPE.
  • adduct The precise nature of the adduct is not known. It may be a salt or complex. In any event, it is readily and conveniently cracked as described hereinafter, to produce THPE of high purity.
  • the alkanol may contain a decolorizing proportion, typically about 0.01-0.10% by weight, of an alkali metal borohydride or dithionite (MBH 4 or M 2 S 2 O 3 , respectively, where M is an alkali metal), as a decolorizing agent; sodium borohydride is preferred.
  • a decolorizing proportion typically about 0.01-0.10% by weight, of an alkali metal borohydride or dithionite (MBH 4 or M 2 S 2 O 3 , respectively, where M is an alkali metal)
  • M alkali metal
  • M 2 S 2 O 3 dithionite
  • the triethylamine may be introduced at a temperature in the range of about 20-40°C. If a relatively large excess of triethylamine (e.g., a molar ratio of triethylamine to THPE of at least about 2:1), the adduct crystallizes slowly. Further crops of adduct may be obtained by allowing the mixture to stand at ambient temperature and/or by adding water, typically in a 1:1 molar ratio to methanol. Smaller proportions of triethylamine will cause adduct to form but it may remain in solution until precipitated by addition of water. When formation and crystallization of a crop of adduct is complete, the adduct may be removed by filtration.
  • a relatively large excess of triethylamine e.g., a molar ratio of triethylamine to THPE of at least about 2:1
  • the adduct may be cracked by heating in vacuum to a temperature of at least 80°C and preferably about 85-100°C, whereupon the triethylamine is easily removed by volatilization.
  • cracking may be achieved by contact with aqueous acid at a temperature in the range of about 20-50°C, preferably about 20-30°C.
  • Typical acids which may be employed are the common mineral acids and acetic acid, at concentrations of about 1-2 M.
  • the free THPE precipitates from the acidic solution and may be recovered by conventional means. Its purity is generally at least about 99% by weight, and its APHA color number is usually no higher than about 200.
  • the adduct was slurried in a 1.5 M aqueous acetic acid solution for 1 hour. Upon filtration, THPE was isolated as a snow white solid.
  • Example 1 The procedure of Example 1 was repeated and water, 250 ml, was added slowly to the mother liquor from the second crop of crystals, resulting in further precipitation of white solid which was collected by filtration. The various crops were washed with water, dried and combined.
  • Example 1 The procedure of Example 1 was repeated, except that the methanol contained 0.05% by weight sodium borohydride.
  • Example 3 The procedure of Example 3 was repeated, using crude THPE prepared by the reaction of phenol with 4-hydroxyacetophenone.
  • Example 2 The procedure of Example 1 was repeated except that the methanol was omitted and the crude THPE was treated with neat triethylamine. Clumps of adduct "crashed" from the mixture.

Abstract

Tris(4-hydroxyphenyl)alkanes such as 1,1,1-tris(4-hydroxyphenyl)ethane are purified by formation of an adduct with a molar excess of a C1-4 primary alkyl tertiary amine, preferably triethylamine. Adduct formation is preferably effected in a polar organic solvent such as methanol. The pure tris(4-hydroxyphenyl)alkane may be recovered from the adduct by thermal or aqueous acid-promoted cracking.

Description

Background of the Invention
This invention relates to the purification of 1,1,1-tris(4-hydroxyphenyl)alkanes and especially 1,1,1-tris(4-hydroxyphenyl)ethane.
The subject compounds, especially the ethane compound which is hereinafter sometimes designated "THPE", are useful as branching agents for polycarbonates. For this purpose, they may be incorporated in reaction mixtures also containing dihydroxyaromatic compounds such as bisphenol A and carbonate sources such as phosgene or diphenyl carbonate. The compounds are commonly prepared by the reaction of 4-hydroxyacetophenone and its homologs with phenol, said reaction being analogous to the reaction of phenol with acetone to form 2,2-bis(4-hydroxyphenyl)propane, also known as "bisphenol A". As disclosed in copending provisional application Serial No. 08/583,264 and complete application Serial No. [RD-24972], the disclosures of which are incorporated by reference herein, a second method for preparing THPE (recovered in admixture with bisphenol A) is by the reaction under acidic conditions of phenol with 2,4-pentanedione.
According to US Patent 4,992,598, THPE produced by the reaction of 4-hydroxyacetophenone with phenol can be purified by a series of washes with methanol-water variously containing at least one of THPE and sodium borohydride. In general, numerous washing steps of this type apparently need to be employed. An alternative purification method which does not require so many steps is desirable.
Summary of the Invention
The present invention provides such an alternative purification method. It may be employed to afford a product having an APHA color number of less than 200 from a crude product containing at least about 90% THPE by weight.
The invention is a method for further purifying a tris(4-hydroxyphenyl)alkane of at least about 90% by weight purity which comprises:
  • forming an adduct by contacting said tris(4-hydroxyphenyl)alkane with a molar excess of a C1-4 primary alkyl tertiary amine, and
  • recovering purified tris(4-hydroxyphenyl)alkane from said adduct by thermal or aqueous acid-promoted cracking.
    • Detailed Description, Preferred Embodiments
    The tris(4-hydroxyphenyl)alkanes which may be purified by the method of this invention include, as a genus, those compounds capable of preparation by the reaction of phenol with 4-hydroxyacetophenone and its higher homologs, such as the corresponding propiophenone and butyrophenone. The preferred compound is THPE.
    According to the invention, THPE having a purity of at least about 90% by weight is first obtained. In the case of the 4-hydroxyacetophenone preparation method, THPE of the required purity may be obtained by removing by-product phenol by filtration after adjusting the water content, as disclosed in the aforementioned U.S. Patent 4,992,598. In the case of the 2,4-pentanedione synthesis method, slurrying in a chlorinated alkane such as methylene chloride followed by filtration can afford a solid product of the requisite purity.
    The essential purification step is the formation of an adduct between THPE and a C1-4 primary alkyl tertiary amine such as trimethylamine, triethylamine or tri-n-butylamine. Triethylamine is preferred and will often be referred to hereinafter; however, it should be understood that other tertiary amines as described may be substituted therefor.
    The adduct is formed by blending the THPE with a molar excess of the amine. A typical molar ratio of amine to THPE is at least about 1.5:1, preferably at least about 2:1 and most preferably about 2.4-2.8:1. The adduct thus formed comprises equimolar proportions of the amine and THPE.
    The precise nature of the adduct is not known. It may be a salt or complex. In any event, it is readily and conveniently cracked as described hereinafter, to produce THPE of high purity.
    It is possible to merely blend the two reagents, THPE and amine, in proportions such that the amine serves as a solvent. However, the adduct then sometimes "crashes" from the mixture in clumps which are difficult to process further. Therefore, it is usually preferred to employ a separate solvent, most often a polar organic liquid such as a C1-4 alkanol; methanol is preferred and is generally referred to hereinafter. The alkanol may contain a decolorizing proportion, typically about 0.01-0.10% by weight, of an alkali metal borohydride or dithionite (MBH4 or M2S2O3, respectively, where M is an alkali metal), as a decolorizing agent; sodium borohydride is preferred.
    After dissolution of the crude THPE in the alkanol, the triethylamine may be introduced at a temperature in the range of about 20-40°C. If a relatively large excess of triethylamine (e.g., a molar ratio of triethylamine to THPE of at least about 2:1), the adduct crystallizes slowly. Further crops of adduct may be obtained by allowing the mixture to stand at ambient temperature and/or by adding water, typically in a 1:1 molar ratio to methanol. Smaller proportions of triethylamine will cause adduct to form but it may remain in solution until precipitated by addition of water. When formation and crystallization of a crop of adduct is complete, the adduct may be removed by filtration.
    Following its isolation, the adduct may be cracked by heating in vacuum to a temperature of at least 80°C and preferably about 85-100°C, whereupon the triethylamine is easily removed by volatilization. Alternatively, cracking may be achieved by contact with aqueous acid at a temperature in the range of about 20-50°C, preferably about 20-30°C. Typical acids which may be employed are the common mineral acids and acetic acid, at concentrations of about 1-2 M. The free THPE precipitates from the acidic solution and may be recovered by conventional means. Its purity is generally at least about 99% by weight, and its APHA color number is usually no higher than about 200.
    The method of the invention is illustrated by the following examples.
    Example 1
    A 500-ml round-bottomed flask equipped with a stirrer was charged with 94 g (1 mole) of phenol, 1.50 g (14 mmol) of 3-mercaptopropionic acid and 100 mg of p-terphenyl as an internal standard. The reaction mixture was warmed to 60°C, whereupon the phenol melted. Hydrogen chloride gas was bubbled through the mixture for 30 minutes, after which it was cooled to room temperature and 8.33 g (83 mmol) of 2,4-pentanedione was added dropwise over 30 minutes. The mixture was heated to 40°C with occasional addition of hydrogen chloride gas, during which time it became very viscous and a precipitate slowly formed. Stirring was continued ovemight at room temperature.
    A portion of the mixture was filtered, yielding an orange solid shown by analysis to be a mixture of THPE and bisphenol A. To the remainder of the mixture was added 300 ml of methylene chloride, whereupon a pink solid precipitated and was collected by filtration. Liquid chromatographic analysis showed the solid to comprise about 92% by weight THPE, 6.1% bisphenol A and 1% phenol.
    A 63.5-g sample of the crude THPE (191 mmol of THPE) was dissolved in 250 ml of methanol to form a light amber solution. Triethylamine, 62.5 ml (449 mmol) was added, whereupon the color of the solution changed to faint pink. A white solid crystallized slowly as the mixture was stirred over 45 minutes. The solid was removed by filtration and was found upon analysis to be the desired adduct of THPE and triethylamine. Upon standing for an additional 2 hours, the filtrate deposited a second crop which was similarly removed by filtration.
    The adduct was slurried in a 1.5 M aqueous acetic acid solution for 1 hour. Upon filtration, THPE was isolated as a snow white solid.
    Example 2
    The procedure of Example 1 was repeated and water, 250 ml, was added slowly to the mother liquor from the second crop of crystals, resulting in further precipitation of white solid which was collected by filtration. The various crops were washed with water, dried and combined.
    Example 3
    The procedure of Example 1 was repeated, except that the methanol contained 0.05% by weight sodium borohydride.
    Example 4
    The procedure of Example 3 was repeated, using crude THPE prepared by the reaction of phenol with 4-hydroxyacetophenone.
    Example 5
    The procedure of Example 1 was repeated except that the methanol was omitted and the crude THPE was treated with neat triethylamine. Clumps of adduct "crashed" from the mixture.
    The results of Examples 1-5 are listed in the following table.
    Example THPE recovery, % THPE purity, % APHA color no.
    1 80 99.4 179
    2 95 99.3 176
    3 86 99.4 63
    4 94 99.5 Light tan
    5 94 99.4 Pink
    It is apparent that the method of the invention produces very pure THPE in high yield. Color is substantially improved by using sodium borohydride.

    Claims (10)

    1. A method for further purifying a tris(4-hydroxyphenyl)alkane of at least about 90% by weight purity which comprises:
      forming an adduct by contacting said tris(4-hydroxyphenyl)alkane with a molar excess of a C1-4 primary alkyl tertiary amine, and
      recovering purified tris(4-hydroxyphenyl)alkane from said adduct by thermal or aqueous acid-promoted cracking.
    2. A method according to claim 1 wherein the tris(4-hydroxyphenyl)alkane is 1,1,1-tris(4-hydroxyphenyl)ethane.
    3. A method according to claim 2 wherein the tertiary amine is triethylamine.
    4. A method according to claim 3 wherein adduct formation is conducted in a polar organic liquid as solvent.
    5. A method according to claim 4 wherein the polar organic liquid is methanol.
    6. A method according to claim 5 wherein the methanol contains a decolorizing proportion of an alkali metal borohydride or dithionite.
    7. A method according to claim 6 wherein the alkali metal borohydride is sodium borohydride.
    8. A method according to claim 3 wherein the molar ratio of triethylamine to 1,1,1-tris(4-hydroxyphenyl)ethane is in the range of about 2.4-2.8:1.
    9. A method according to claim 3 wherein multiple crops of adduct are caused to precipitate.
    10. A method according to any preceding claim wherein cracking of said adduct is effected (1) by heating in vacuum to a temperature of at least 80°C, whereupon the triethylamine is removed by volatilization, or (2) by contact with aqueous acid at a temperature in the range of about 20-50°C.
    EP97307106A 1996-09-27 1997-09-12 Method for purifying 1,1,1-tris (4-Hydroxyphenyl)-alkanes Expired - Lifetime EP0832868B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    US08/722,282 US5672776A (en) 1996-09-27 1996-09-27 Method for purifying 1,1,1-tris(4-hydroxyphenyl)-alkanes
    US722282 1996-09-27

    Publications (3)

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    EP0832868A2 true EP0832868A2 (en) 1998-04-01
    EP0832868A3 EP0832868A3 (en) 1999-03-17
    EP0832868B1 EP0832868B1 (en) 2001-09-26

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    US (1) US5672776A (en)
    EP (1) EP0832868B1 (en)
    JP (1) JP3944283B2 (en)
    DE (1) DE69706933T2 (en)
    ES (1) ES2164305T3 (en)
    SG (1) SG53073A1 (en)

    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP2374785A1 (en) * 2010-04-07 2011-10-12 Bayer MaterialScience AG Purification of tris-hydroxyaryl connections

    Families Citing this family (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US20060004214A1 (en) * 2004-06-30 2006-01-05 Gurram Kishan Methods for preparing 1,1,1-tris(4-hydroxyphenyl)alkanes
    US7304189B2 (en) * 2005-01-31 2007-12-04 General Electric Company Methods for preparing 1,1,1-tris(4-hydroxyphenyl)alkanes
    US8343608B2 (en) 2010-08-31 2013-01-01 General Electric Company Use of appended dyes in optical data storage media
    CN113461493B (en) * 2021-07-01 2022-08-05 万华化学集团股份有限公司 Preparation method of 1,1, 1-tri (4-hydroxyphenyl) ethane

    Citations (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US4992598A (en) * 1990-02-09 1991-02-12 Hoechst Celanese Corporation Purification of 1, 1, 1-tris(4'-hydroxyphenyl)ethane
    EP0567338A2 (en) * 1992-04-23 1993-10-27 General Electric Company Method of phenol extraction from phenol tar

    Family Cites Families (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US5130467A (en) * 1990-08-31 1992-07-14 Hoechst Celanese Corporation Acrylate esters of 1,1,1-trishydroxyphenylethane
    US5202505A (en) * 1992-03-24 1993-04-13 Hoechst Celanese Corporation Purification of hydroxyphenyl alkanes

    Patent Citations (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US4992598A (en) * 1990-02-09 1991-02-12 Hoechst Celanese Corporation Purification of 1, 1, 1-tris(4'-hydroxyphenyl)ethane
    EP0567338A2 (en) * 1992-04-23 1993-10-27 General Electric Company Method of phenol extraction from phenol tar

    Cited By (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP2374785A1 (en) * 2010-04-07 2011-10-12 Bayer MaterialScience AG Purification of tris-hydroxyaryl connections
    EP2374784A1 (en) * 2010-04-07 2011-10-12 Bayer MaterialScience AG Purification of tris-hydroxyaryl connections
    US8507732B2 (en) 2010-04-07 2013-08-13 Bayer Intellectual Property Gmbh Purification of tris-hydroxyaryl compounds

    Also Published As

    Publication number Publication date
    EP0832868A3 (en) 1999-03-17
    ES2164305T3 (en) 2002-02-16
    SG53073A1 (en) 1998-09-28
    EP0832868B1 (en) 2001-09-26
    US5672776A (en) 1997-09-30
    JP3944283B2 (en) 2007-07-11
    DE69706933D1 (en) 2001-10-31
    JPH10158206A (en) 1998-06-16
    DE69706933T2 (en) 2002-04-25

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